CN116356190B - High-strength high-plasticity Gao Liewen capacity limit high-entropy alloy and preparation method thereof - Google Patents
High-strength high-plasticity Gao Liewen capacity limit high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-strength high-plasticity Gao Liewen capacity limit high-entropy alloy and a preparation method thereof, wherein the alloy comprises the following constituent elements in percentage by atom: 29-31% of Mn, 9-11% of Cr, 9-11% of Si, 0.8-1.6% of C, and the balance of Fe and unavoidable impurity elements; the ratio of atomic percentages of C and Si in the alloy is not higher than 0.178; the volume fraction of the face centered cubic structured phases in the alloy exceeds 95%. The preparation method comprises induction smelting, homogenizing annealing treatment, hot rolling treatment and solution treatment. The high-entropy alloy provided by the invention has the advantages of low raw material cost, easiness in preparation and processing, high strength, high plasticity and high crack tolerance.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloy materials, and particularly relates to a high-strength high-plasticity Gao Liewen-capacity high-entropy alloy and a preparation method thereof.
Background
Because of the unique multi-principal element characteristics, the high-entropy alloy has a plurality of performances exceeding the traditional alloy, including good low-temperature fracture toughness, high-temperature strength, structural stability and the like, and is expected to solve the bottleneck problem of material performance in various fields at present, thereby meeting the higher requirements of development of high-end manufacturing industry on the material performance. For the last decade, high-entropy alloys based on face-centered cubic phases have received considerable attention because of the variety of plastic deformation mechanisms that can be achieved by the manipulation of stacking faults. By reducing the stacking fault energy below a certain value, the alloy can have a twinning induced plasticity effect and/or a transformation induced plasticity effect, and the two effects can significantly improve the work hardening capacity, the tensile strength, the plasticity and the crack tolerance of the alloy. However, previous studies have shown that face-centered cubic high entropy alloys with twinning and/or transformation induced plasticity effects tend to exhibit very low yield strengths, which severely limits their potential application value.
The addition of element C to face-centered cubic structured high entropy alloys has proven to be an effective means of increasing the yield strength of such alloys. On the one hand, because C is a gap solid solution element, the solution strengthening effect is very strong; on the other hand, because the solid solubility of C is limited, brittle phases such as sigma, mu, laves and the like are easily precipitated in the alloy, so that a strong precipitation strengthening effect is generated. However, the addition of the element C also can obviously improve the stacking fault energy of the alloy, and when the content of C exceeds a certain value, the twinning and phase change induced plasticity effect in the alloy can be completely inhibited. Moreover, when a brittle phase is inevitably generated in such an alloy, the brittle phase often cracks quickly during deformation, and the corresponding crack is easily propagated to the face-centered cubic structural phase around it, resulting in the generation of microcracks in the face-centered cubic structural phase, and the microcracks are continuously propagated with the increase of the deformation amount, eventually leading to failure fracture. Clearly, the addition of element C, while significantly improving the strength of the face-centered cubic high entropy alloy, also tends to result in significant reductions in work hardening capacity, tensile strength, plasticity and crack tolerance. Therefore, the content of the C element in the face-centered cubic structure high-entropy alloy with the twinning and/or transformation induced plasticity effect is reasonably controlled, so that the alloy can still have the twinning and/or transformation induced plasticity effect after the C element is added, and the alloy is a key way for improving the yield strength of the alloy and simultaneously retaining the high plasticity and the high crack tolerance of the alloy.
Based on the alloy, the application provides a high-strength high-plasticity Gao Liewen-capacity high-entropy alloy and a preparation method thereof.
Disclosure of Invention
Considering the problem that the yield strength is low in common in the high-plasticity and Gao Liewen-capacity high-entropy alloy with the twinning and/or phase-change induced plasticity effect, the addition of the C element can easily inhibit the twinning and phase-change induced plasticity effect and obviously reduce the plasticity and crack tolerance of the alloy despite the fact that the yield strength can be improved, the development of the high-entropy alloy which can still keep the twinning and/or phase-change induced plasticity effect after being strengthened by the addition of the C element is a key way for solving the application limitation of the existing high-plasticity and Gao Liewen-capacity high-entropy alloy.
Based on the above consideration, the invention provides a high-strength high-plasticity Gao Liewen tolerance high-entropy alloy and a preparation method thereof, aiming at the problem that the yield strength of the high-plasticity and Gao Liewen-capacity high-entropy alloy with twinning and/or phase change induced plasticity effect is generally low.
The invention is realized by the following technical scheme:
The first aspect of the invention provides a high-strength high-plasticity Gao Liewen capacity limit high-entropy alloy, which comprises the following constituent elements in percentage by atom: 29% -31% of Mn,9% -11% of Cr,9% -11% of Si,0.8% -1.6% of C, and the balance of Fe and unavoidable impurity elements;
Wherein the ratio of atomic percentages of C and Si in the high entropy alloy is not higher than 0.178; to ensure that the stacking fault energy of the face centered cubic phase in the alloy is below 18mJ/m 2 so that it still has twinning and/or transformation induced plasticity effects after addition of the element C, thereby preserving its high plasticity and high crack tolerance while increasing the yield strength of the alloy.
As a further illustration of the present invention, the atomic percent of C in the high entropy alloy may be, for example, 0.8%, 0.88%, 1.50%, 1.6% C, etc.; the atomic percentage of Si may be, for example, 9%, 10.53%, 10.97%, 11%, or the like.
As a further illustration of the present invention, the volume fraction of the face centered cubic phase in the high entropy alloy is greater than 95% to ensure that the alloy has a high crack tolerance.
As a further explanation of the present invention, the high-entropy alloy has a yield strength of 330MPa or more, a tensile strength of 800MPa or more, and a crack tolerance of 40% or more.
In a further aspect, the invention provides a method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to any one of the above, wherein the preparation method comprises induction smelting, homogenizing annealing treatment, hot rolling treatment and solution treatment.
As a further explanation of the present invention, the preparation method uses pure Fe, pure Mn, pure Cr, pure Si, pure C with purity higher than 99.5% as raw materials.
As a further illustration of the invention, the induction smelting is performed in a vacuum in a frequency induction smelting furnace and argon is used as a protective atmosphere.
As a further explanation of the invention, the induction smelting is repeatedly performed for 3-5 times, wherein after each smelting is completed, the alloy ingot is turned over first and then the next smelting is performed, so that the component uniformity of the finally obtained finished ingot is improved.
As a further explanation of the invention, the homogenizing annealing treatment is water-cooling quenching after heat preservation for 12 hours at 1100 ℃ under the protection of argon gas so as to ensure uniform distribution of various alloy elements.
As a further explanation of the invention, the hot rolling treatment is to adopt a double-roller plate and strip mill to carry out multi-pass rolling after heat preservation and heat penetration in air at 900 ℃, the deformation rate of each pass is 15-25%, and the hot rolling treatment is carried out by returning to a furnace at 900 ℃ for 5-10 min after each pass before the last pass is finished so as to ensure that no obvious surface cracks are generated; the total hot rolling deformation rate is 65-70% so as to ensure that the cast structure is fully broken and shrinkage porosity and shrinkage cavity are fully closed.
As a further explanation of the invention, the solution treatment is water-cooling quenching after heat preservation for 20-60 min at 1100 ℃ under the protection of argon gas so as to ensure that a complete recrystallization structure is formed.
Compared with the prior art, the invention has the following advantages:
the high-strength high-plasticity Gao Liewen capacity limit high-entropy alloy prepared by the method has low cost, is easy to prepare and process, has yield strength of more than 330MPa and tensile strength of more than 800MPa after simple solution treatment, has crack tolerance of more than 40%, and is particularly suitable for manufacturing large structural members with higher requirements on strength, plasticity and crack tolerance.
Drawings
FIG. 1 is an initial tissue scanning electron microscope photograph of the high-entropy alloy prepared in examples 1-2 and comparative example 3 of the present invention;
FIG. 2 is a graph showing the room temperature engineering stress-engineering strain curve of the high-entropy alloy prepared in examples 1-2 and comparative example 3;
FIG. 3 is a scanning electron microscope image of the high-entropy alloy prepared in example 2 of the present invention after 3% tensile deformation and complete fracture.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The high-strength high-plasticity Gao Liewen capacity limit high-entropy alloy of the embodiment comprises the following main constituent elements in atomic percent: 47.77% Fe,30.39% Mn,10.00% Cr,10.97% Si,0.88% C. The atomic percent ratio of C and Si in the alloy is 0.080, and the stacking fault energy is 14.18mJ/m 2.
The preparation method of the alloy comprises the following steps:
S1, taking pure Fe, pure Mn, pure Cr, pure Si and pure C with purity higher than 99.5% as raw materials, adopting argon as protective atmosphere, and smelting in a vacuum frequency induction smelting furnace.
S2, turning over the cast ingot obtained by the smelting in the previous step, and adopting the same parameters to carry out remelting, and repeating the smelting for 3 times.
S3, placing the finished cast ingot into a heat treatment furnace with argon protection, heating to 1100 ℃ along with the furnace, carrying out homogenizing annealing treatment for 12 hours, and then carrying out water cooling quenching.
S4, cutting the ingot subjected to the homogenizing annealing treatment into plates by adopting a wire electric discharge machine, heating the plates to 900 ℃, preserving heat and thoroughly, adopting a double-roller plate and strip mill to roll for multiple passes, wherein the deformation rate of each pass is 20-25%, and returning to the furnace for preserving heat for 8-10 min at 900 ℃ after each pass before the last pass is finished, wherein the total hot rolling deformation rate is 68%.
S5, placing the plate subjected to the hot rolling treatment in a heat treatment furnace protected by argon, carrying out solution treatment at 1100 ℃ for 20min, and then carrying out water cooling quenching.
The initial structure of the alloy prepared in this example was characterized by scanning electron microscopy and the results are shown in FIG. 1. It can be seen from the figure that the alloy prepared in this example consisted of 100% face-centered cubic phase.
According to GB/T228.1-2010 section 1 Metal Material tensile test: the mechanical properties of the alloy prepared in this example were measured by room temperature test method, and the results are shown in FIG. 2. The result shows that the yield strength is 331MPa, the tensile strength is 802MPa, and the elongation after fracture is 76.2%.
Examples
The main constituent elements and atomic percentages of the high-strength high-plasticity high-fracture-tolerance high-entropy alloy are as follows: 47.51% Fe,30.48% Mn,9.98% Cr,10.53% Si,1.50% C. The atomic percent ratio of C and Si in the alloy is 0.142, and the stacking fault energy is 16.50mJ/m 2.
The preparation method of the alloy comprises the following steps:
S1, taking pure Fe, pure Mn, pure Cr, pure Si and pure C with purity higher than 99.5% as raw materials, adopting argon as protective atmosphere, and smelting in a vacuum frequency induction smelting furnace.
S2, turning over the cast ingot obtained by the smelting in the previous step, and adopting the same parameters to carry out remelting, and repeating the smelting for 3 times.
S3, placing the finished cast ingot into a heat treatment furnace with argon protection, heating to 1100 ℃ along with the furnace, carrying out homogenizing annealing treatment for 12 hours, and then carrying out water cooling quenching.
S4, cutting the ingot subjected to the homogenizing annealing treatment into plates by adopting a wire electric discharge machine, heating the plates to 900 ℃, keeping the temperature and heating thoroughly, adopting a double-roller plate and strip mill to roll for multiple passes, wherein the deformation rate of each pass is 20-25%, and returning to the furnace for keeping the temperature at 900 ℃ for 8-10 min after each pass before the last pass is finished. The total hot rolling deformation rate is 68%;
S5, placing the plate subjected to the hot rolling treatment in a heat treatment furnace protected by argon, carrying out solution treatment at 1100 ℃ for 60min, and then carrying out water cooling quenching.
The initial structure of the alloy prepared in this example was characterized by scanning electron microscopy and the results are shown in FIG. 1. As can be seen from the figure, the alloy prepared in this example consists of a face-centered cubic phase and a beta-Mn phase, the volume fraction of which is 96.24%.
According to GB/T228.1-2010 section 1 Metal Material tensile test: the mechanical properties of the alloy prepared in this example were measured by room temperature test method, and the results are shown in FIG. 2. The result shows that the yield strength is 400MPa, the tensile strength is 841MPa, and the elongation after fracture is 47.8%.
The structure of the alloy prepared in this example after 3% tensile deformation and complete fracture was analyzed by scanning electron microscopy, and the result is shown in fig. 3. As can be seen from fig. 3, the alloy starts to generate micro cracks in the β -Mn grains after 3% elongation deformation, and the surface micro cracks are more numerous and wider after complete fracture, and the crack tolerance of the alloy is 44.8% in combination with the elongation after fracture.
Comparative example 3
The high-entropy alloy of the comparative example comprises the following main constituent elements in atomic percent: 49.36% Fe,29.76% Mn,9.97% Cr,10.86% Si,0.05% C.
The preparation method of the alloy comprises the following steps:
s1, taking pure Fe, pure Mn, pure Cr and pure Si with purity higher than 99.5% as raw materials, adopting argon as protective atmosphere, and smelting in a vacuum frequency induction smelting furnace;
s2, turning over the cast ingot obtained by the smelting in the previous step, and adopting the same parameters to carry out remelting, and repeating the smelting for 3 times;
s3, placing the finished cast ingot into a heat treatment furnace with argon protection, heating to 1100 ℃ along with the furnace, carrying out homogenizing annealing treatment for 12 hours, and then carrying out water cooling quenching.
S4, cutting the ingot subjected to the homogenizing annealing treatment into plates by adopting a wire electric discharge machine, heating the plates to 900 ℃, preserving heat and thoroughly, and then adopting a double-roller plate and strip mill to roll for multiple passes, wherein the deformation rate of each pass is 20-25%, and the ingot is returned to the furnace for preserving heat for 8-10 min at 900 ℃ after each pass before the last pass is finished, and the total hot rolling deformation rate is 68%;
S5, placing the plate subjected to the hot rolling treatment in a heat treatment furnace protected by argon, carrying out solution treatment at 1100 ℃ for 60min, and then carrying out water cooling quenching.
The initial structure of the alloy prepared in this comparative example was characterized by a scanning electron microscope, and the results are shown in fig. 1. As can be seen from the figure, the alloy prepared in this comparative example consisted of 100% face-centered cubic phase.
According to GB/T228.1-2010 section 1 Metal Material tensile test: the room temperature test method measures the mechanical properties of the alloy prepared in this comparative example, and the results are shown in figure 2. The result shows that the yield strength is 261MPa, the tensile strength is 669MPa, and the elongation after fracture is 69.8%. The content of element C in the alloy composition of this comparative example was outside the scope of the patent protection, compared to examples 1 and 2, resulting in a significantly lower yield strength than examples 1 and 2.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The high-strength high-plasticity Gao Liewen-volume-limit high-entropy alloy is characterized by comprising the following components in percentage by atom: 29% -31% of Mn,9% -11% of Cr,9% -11% of Si,0.8% -1.6% of C, and the balance of Fe and unavoidable impurity elements; wherein the ratio of atomic percentages of C and Si in the high entropy alloy is not higher than 0.178; the volume fraction of the face-centered cubic structure phase in the high-entropy alloy is more than 95%; the yield strength of the high-entropy alloy is above 330MPa, the tensile strength is above 800MPa, and the crack tolerance is above 40%.
2. A method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 1, wherein the preparation method comprises induction smelting, homogenizing annealing treatment, hot rolling treatment and solution treatment.
3. The method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 2, wherein the preparation method uses pure Fe, pure Mn, pure Cr, pure Si and pure C with purity higher than 99.5% as raw materials.
4. The method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 2, wherein the induction smelting is performed in a vacuum frequency induction smelting furnace and argon is adopted as a protective atmosphere.
5. The method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 2, wherein the induction smelting is repeated for 3-5 times, and each smelting is completed by turning over an alloy ingot and then smelting the next time.
6. The method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 2, wherein the homogenizing annealing treatment is water-cooling quenching after heat preservation for 12 hours at 1100 ℃ under the protection of argon.
7. The method for preparing the high-strength high-plasticity Gao Liewen capacity-limit high-entropy alloy according to claim 2, wherein the hot rolling treatment is that after heat preservation and heat penetration in air at 900 ℃, a double-roller plate and strip mill is adopted for multi-pass rolling, the deformation rate of each pass is 15-25%, the furnace is returned for heat preservation at 900 ℃ for 5-10 min after each pass before the last pass is finished, and the total hot rolling deformation rate is 65-70%.
8. The method for preparing the high-strength high-plasticity Gao Liewen-capacity high-entropy alloy according to claim 2, wherein the solid solution treatment is water-cooling quenching after heat preservation for 20-60 min at 1100 ℃ under the protection of argon.
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| CN101104908A (en) * | 2007-08-06 | 2008-01-16 | 大连海事大学 | Iron-base shape memory alloy locked key and its manufacturing and using method |
| KR20150105623A (en) * | 2015-09-07 | 2015-09-17 | 주식회사 포스코 | Material for submerged arc welding and gas metal arc welding having excellent impact resistance and abrasion resistance properties |
| CN112853230A (en) * | 2021-01-08 | 2021-05-28 | 西北工业大学 | Low-layer-dislocation-energy face-centered cubic structure high-entropy shape memory alloy and preparation method thereof |
| CN115044830A (en) * | 2022-06-07 | 2022-09-13 | 西北工业大学 | Light TWIP steel based on twinning induced plasticity and ordered reinforcement and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101104908A (en) * | 2007-08-06 | 2008-01-16 | 大连海事大学 | Iron-base shape memory alloy locked key and its manufacturing and using method |
| KR20150105623A (en) * | 2015-09-07 | 2015-09-17 | 주식회사 포스코 | Material for submerged arc welding and gas metal arc welding having excellent impact resistance and abrasion resistance properties |
| CN112853230A (en) * | 2021-01-08 | 2021-05-28 | 西北工业大学 | Low-layer-dislocation-energy face-centered cubic structure high-entropy shape memory alloy and preparation method thereof |
| CN115044830A (en) * | 2022-06-07 | 2022-09-13 | 西北工业大学 | Light TWIP steel based on twinning induced plasticity and ordered reinforcement and preparation method thereof |
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